Hair control compositions and method of use

ABSTRACT

A hair control preparation, particularly an aerosol hairspray, comprises a solution of a film-forming resin and a normally solid plasticiser for the resin which gradually volatilises from the resin after the hair control preparation has been applied to the hair, the weight ratio of resin to volatile plasticiser being from 1:2 to 20:1.

United States Patent Flawn et al.

HAIR CONTROL COMPOSITIONS AND METHOD OF USE Inventors: Richard EdwinFlawn, Shepperton; Malcolm Richard Neam, Camberley; Peter John Petter,Maidenhead, all of England Assignee: Lever Brothers Company, New

York, NY.

Filed: Dec. 7, 1972 Appl. No.1 313,077

Foreign Application Priority Data Dec. 8, 1971 Great Britain 56968/71U.S. Cl..l 424/47, 424/71 Int. Cl A6lk 7/10 Field of Search 424/71, 47

[56] References Cited UNITED STATES PATENTS 3,400,198 9/1968 Lang 424/713,723,616 3/1973 Erlemann et a1. 424/71 Primary Examiner-Sam RosenAttorney, Agent, or Firm-Louis F. Kline, Jr.

[ 5 7] ABSTRACT 8 Claims, No Drawings HAIR CONTROL COMPOSITIONS ANDMETHOD OF USE This invention relates to hair preparations, and moreparticularly to hair control preparations for holding the hair in adesired configuration. Preparations of this .kind include hair settinglotions and hairsprays, the

hairsprays, who use the productsfrequently find thatthe resin depositedon the hair tends to build up despite brushing of the hair betweenapplications and that as a consequence the hair becomes progressivelymore difficult to comb and brush out. Furthermore, this accu-' 1mulation of resin gives the hair an unnatural feel. One

can, of course, mitigate this disadvantage by applying less resin to thehair, but this, however, results in less hold being obtained.

1n the work leading up ,to the present invention we found that theresins which have the better hair retaining properties are those which.are relatively flexible whereas those which are the more easily combedor brushed out of the hair'are the more brittle resinsaln other words,those resins having the lower glass transition temperatures (Tg) havethe better hold characteristics and those of higher glass transitiontemperatures have the better comb-out properties.

We have now discovered that improved hair control preparations can beformulated by including along with resin a resin-modifying agent whichis normally solid (i.e.', is solid at 20 C) and which softens the resinand improves its initial holding properties but which over a relativelyshortperiod of time, say within hours, volatilises from the hairwherebythe resin is gradually converted into a form in which it is more easilycombed out of the hair.

Accordingly the invention provides a hair control preparation comprisinga solution of a film-forming resin and a normally solid material whichplasticises the resin and which gradually volatilises from the resinafter applying the preparation to the hair, the weight ratio of resin tovolatile plasticiser being from 1:2 to :1.

An advantage of the invention is that by the use of the volatileplasticiser one can improve the initial holding properties of the resin(matching that obtainable with acornparable or even greater amount of asofter resin) and produce a resin deposit which develops over a periodof time an improved ease of removal as the plasticiser volatilises fromthe hair. From another aspect, the use of a volatile plasticiser inaccordance with the invention permits one to improve the initial holdproperties of a hair preparation without increasing the amount of theresin in the preparation: an increase in the amount of the resin wouldresult in more resin being applied to the hair with the consequence thatthe hair would be more difficult to comb out.

The film-forming resins used in preparations in accordance with theinvention desirably have glass transition temperatures (Tg) of at least20 C. The use of the Tg is a common way of characterising resins and isdescribed for example by Burrell, H in Official Digest, 34, 131 (1962).It can be determined by the technique known as Differential ThermalAnalysis (see, for example, the method of Keavney, JJ and Eberlin, EC inJ.Appl.Polymer Sci., 3 47 (1960). A high Tg is an indication of thebrittleness of a resin.'ln accordance with our finding that the morebrittle the resin the more easily it is combed out of the hair,thepreferred resins used in hair compositions of this invention are thosehaving a Tg of at least 35 C and usually no more than 150 C.

Compatible Volatile Resin Plasticisers LUVlSKOL VA 28l propionamide (acopolymer containing benzoic acid 20% vinyl pyrrolidone and salicylicacid vinyl acetate having menthol a Tg value of 42C and thymol suppliedas a 50% solution in isopropanol) methyl-Lnaphthylketone LUVISKOL VA 37Epropionamide (a copolymer containing benzoic acid 30% vinyl pyrrolidoneand salicylic acid 70%'vinyl acetate having hexachloroethane a Tg valueof 65C and benzophenone supplied as a 50% solution in ethanol Acopolymer containing propionamide about 43% rnethacrylic acetamide acidand about 57% hexachloroethane methyl acrylate having benzo'phenone a Tgvalue of 95C We have also found that propionamide is also a suitablevolatile plasticiser for use with the following reslnSZ Resin Tg Value""C Bina 405, an acrylic ester amide copolymer containing carboxyl groupsNational Starch Resyn 28-1310, a copolymer of vinyl acetate and crotonicacid Aristotlex C, a copolymer of vinyl acetate and crotonic acid VEM640 M48, a vinyl terpolymer containing ester, acrylic and carboxylgroups (supplied as a 48% solution in ethanol) Gantrez ES 225, acopolymer of methyl vinyl ether and monoethyl ester of maleic acid(supplied as a 50% solution in ethanol) Gantrez ES 335-l, a copolymer ofmethyl vinyl ether and monoisopropyl ester of maleic acid (supplied as a50% solution in isopropanol) Gantrez ES 435, a copolymer of methyl vinylether and monobutyl ester of maleic acid (supplied as a 50% solution inisopropanol) as determined by the Keavney et al. method) 3 The vapourpressures at a temperature of 25 C and at a pressure of 760 mm Hg of thevolatile plasticisers referred to above are as follows:

Vapour Pressure estimated values It is to be understood that theinvention is not limited solely to the resin/volatile plasticisercombinations specifically referred to above. Some experimentation may benecessary in order to select other suitable combinations of resin andnormally solid volatile plasticiser for use in the present invention. Aplasticiser for one resin is not necessarily suitable for plasticisinganother resin. For instance, benzophenone, when used with resinsobtained by copolymerising vinyl pyrrolidone with no more than an equalamount of vinyl acetate (and with certain other water-soluble resins) isreported in British Patent Specification No. 868,879 to result in astiffening of the resin (i.e., the opposite of a plasticising effeet).

The film-forming resin and the volatile plasticiser are both present inthe hair preparation as a solution in a mutually suitable solvent. As anexample, the solvent can be a volatile organic solvent such as analcohol, especially ethanol, isopropanol or 2-methoxyethanol: methylenechloride is also a suitable volatile organic solvent.

The weight ratio of film-forming resin to volatile plasticiser in thehair preparation according to the invention is from 1:2 to :1. Byappropriate choice of the ratio of resin to plasticiser and of thecontent of resin in the solution, it is possible to obtain hairpreparations which differ widely in their properties.

- At low resimplasticiser ratios, the difference between the degreeofhold exerted by the hair preparation initially and that exerted whenthe majority of the plasticiser has volatilised is quite marked, whereasat-high resinzplasticiser ratios the difference between the initial holdand the hold at a later time is less marked.

The preferred weight ratio of film-forming resin to volatile plasticiseris from 1:1 to 10:1.

The amount of resin present in the solution will depend on the degree ofhold the product is intended to produce and will usually be from 1 to 10percent by weight of the solution.

The hair preparation is preferably in the form of an aerosol hairspray.In this case the solvent, especially one of those previouslyexemplified, the film-forming resin and the volatile plasticiser will bepresent in an aerosol dispenser together with a suitable aerosolpropellant, usually a liquefied normally gaseous substance. Commonlyused propellants are trichlorofluoromethane (propellant l 1) anddichlorodifluoromethane (propellant 12) but others may be employed.Suitable propellants and propellant mixtures 4 for use with hairspraysare well known tothose in the art.

Aerosol hairspray preparations in accordance with the invention willcomprise concentrate and propellant in the usual ratios, generally fromabout 2:1 to 1:5 with the concentrate having typically-the followingcomposition:

% by weight Resin 1 to 10 Volatile plasticiser 0.05 to 10 Perfume 0.3 to1 Solvent balance to In aerosol hairsprays, the amount by weight ofresin based on the total weight of hairspray is usually from 0.5 to 4.0percent.

In further embodiments of the hair control preparation of the inventionother than those based on an aerosol formulation, the preparation maysimply be in the form of a solution of the resin and plasticiser in thesolvent, for example in the weight proportions as set out for the aboveconcentrate. In other product forms, particularly for hairsetting-lotions, an aqueous alcoholic solvent can be used. In certainother cases it might also be possible to use water as the solvent,although the presence of a volatile organic solvent is preferred to givea quick drying product. Other conventional ingredients can beincorporated, if desired, for example a denaturant for ethanol.

, In accordance with a further aspect of the invention, a process isprovided for treating human hair to impart hold to a desired style andsubsequently to facilitate the brush out property of the hair as thehold diminishes by applying to the hair a hair control preparation ofthe type defined herein.

Examples of hair control preparations in accordance with the inventionwill now be described. Percentages are by weight.

EXAMPLE 1 A hairspray of lotion was prepared having the followingcomposition:

Luviskol VA 3715 (50% solution in ethanol) 6.0 Propionamide 0.6 Perfume0.5 Denaturant 0.2 Industrial methylated spirit to 100.0

' 1 EXAMPLE 2 An aerosol hairspray was prepared having the followingcomposition:

EXAMPLE 3 An aerosol hairspray was prepared having the followingcomposition:

5 Luviskol VA 37E (50% solution in ethanol) 4.0 Benzoic acid 0.4 Perfume0.2 Denaturant 0.1 Industrial methylated spirit 35.3 Propellant 11 39.0Propellant 12 to 100.0

-Continued Perfume 0.20 2-methoxyethanol 6.00 Methylene chloride 36.21Propellant 11 27.50 Propellant 12 to 100.00

The following Tests illustrate in vitro and in vivo experiments wherehair control preparations according to the invention were applied tohair and certain properties of the hair were evaluated over a period ofa few hours as the plasticiser volatilised from the resin. In twoEXAMPLE 4 An aerosol hairspray was prepared having the follow- 15 ingcomposition:

2-amino-2-methyl-l-propancil is present as a neutralizing a en tqtthsr so-r .3

EXAMPLE 6 An aerosol hairspray was prepared having the follow- 4 ingcomposition:

experiments, control data where a plasticiser was omitted from the hairpreparation is also provided for comparison.

TEST 1 The following experiment showed the variation with time of theresistance to combing of hair switches when sprayed with an aerosolhairspray of the following composition: I

Copolymer 2.0 Plasticiser 0.4 Industrial methylated spirit 37.6Propellant l1 39.0 Propellant 12 to 100.0

Containing about 43% of methacrylic acid and about 57% of methylacrylate switches of 28 cms' length, prepared from untreated Italianhair fitted with clips at each end were sprayed with the above aerosolhairspray for a predetermined time so that the same amount of resin wassprayed onto each switch. After various intervals of time four of theswitches were taken and each switch drawn through a comb five times andan average combining resistance value determined for the switches. In

this experiment, the comb used was one which had a r strain gaugetransducer cemented. onto the back of it and the varying resistanceproduced by varying strains on the gauge as the hair travelled throughthe comb was processed electronically. During the determination of thecombing resistance value, the hair switches were in a cabinet maintainedat a temperature of 23 C and a Propionamide 0.24 Farms 20 relativehumidity of 35 percent. Denawyam (H0 The combing resistance values givenbelow have Industrial methylated spirit 38.26 b d n Propellant 11 9, eencorrecte to a ow for any variation in resistance Propellant 12 to100.00' to combing of the untreated switches, so that the values ivenare a measure in em irica u r EXAMPLE 7 g p l mts, of the 111C ease inwork required to comb the hair due to the applied An aerosol hairspraywas prepared having the followh i ing composition: The above testprocedure was carried out on a number of compositions containingdifferent plasticisers National Starch Resyn 28-1310 2.00 and theresults are gwen m Table 2 2 1 We have found that the hold of the hairas udged by Propionamide (140 users correlates well with the combingresistance.

TABLE 1 Time of Measurement Combing Resistance value of CombingResistance Plasticiser Benzophenone Hexachloroethane AcetamidePropionamide 1 hour after spraying 195 195 225 130 2 hours afterspraying 180 175 150 3 hours after spraying 170 145 95 4 hours afterspraying 160 1 10 85 125 105 80 5 hours after spraying TEST- 2 A similartest was carried out with an aerosol hairspray of the followingcomposition and the results are given in Table II.

Luviskol 37E (50% solution in ethanol) 4.0 Plasticiser 0.4 Perfume 0.2lndustrial methylated spirit 35.4 Propellant l 1 39.0 Propellant 12 to100.0

A similar comparison of the results for products B and C showed thepreferences as set out in Table lVb.

TABLE II Time of Measurment Combing Resistance Value of CombingResistance Plasticiser Propionamide Hexachloroethane Benzoic AcidSalicylic Acid 1 hour after spraying 170 180 114 256 2 hours afterspraying 166 155 I10 200 3 hours after spraying 164 130 107 145 5 hoursafter spraying 160 82 92 132 8 hours after spraying 92 85 54 120 TEST 3TABLE lVb A further test, similar to those described above, was aperformed to demonstrate the effect on combing resiszzg i g tance at twohourly intervals after spraying of variation in the resinzplasticiserratio. The test products used had Hlding PR B C Lack of stiffness B l in100 following formula- Ease of brushing B 1 in 20 Z Stickiness afterbrushing B l in 10 Copolymer used in Test 1 Propionamide 2.4 ldt'lth1td"t 37.6 ,f "}i y e 393 Thus the addition of propionamide to alightly hold- Propellant 1; to 100.0 ing resin allowed the superior holdof the control (product C) tobe matched while retaining the superior Theresults are given In Table 111- case of brushing and feel after brushingof the lighter holding resin (in product B).

TABLE III 40 TEST 5' Combing Resistance Value ResinzPlasticiser after(wt. ratio) 2 hours 4 hours 6 hours For a comparative product containing2.4 percent of the resin and no plasticiser, the combing resistancevalue was constant with time at 88 units.

TEST 4 Two experimental hairsprays, one containing 2.4 percent ofLuviskol VA 37E solution (Product A), the other containing 2.4 percentof Luviskol VA 37E solution together with 0.24 percent of propionamide(product B), were compared with a commercial hairspray containing 2.25percent of National Starch Resyn 28-1310 (product C) in a user paneltest involving 80 women. All the women used each of the three productsfor a two week period, at the end of which they completed aquestionnaire on the performance of the hairspray.

Comparison of the results for products A and C showed the preferences asset out in Table [Va The following experiment was performed toinvestigate the loss by volatilisation of propionamide from a film ofLuviskol VA 37E resin plasticized with this .,vg l atile material.

TABLE V Time of Analysis by weight of propionamide after sprayingpresent in resin sample 30 mins 14.9 50 mins 6.7 mins 4.1 mins 2.3 20hours 0.5

What is claimed is: 1. A hair control preparation for imparting hold tothe hair yet enabling the hair subsequently to be easily brushed out asthe hold diminishes, said hair control preparation comprising a solutionof i. from about 1 percent to about percent by weight of a film-formingresin having a glass transition temperature of from about 20 C to about150 C,

ii. a plasticiser for the resin which is a solid and which has a vapourpressure at a temperature of 25 C and a pressure of 760 mm Hg of fromabout 0.0000] mm to 2 mm Hg, and which gradually volatilises from theresin thereby diminishing the hold property of the preparation, afterapplying the preparation to the hair, and the weight ratio offilm-forming resin to volatile plasticiser being from 2. The haircontrol preparation as claimed in claim 1, wherein the resin is acopolymer of vinyl pyrrolidone and vinyl acetate containing at least 70percent by weight of vinyl acetate.

3. The hair control preparation as claimed in claim 1, wherein the resinis a copolymer of vinyl acetate and crotonic acid. v

4. The hair control preparation as claimed in claim 2, wherein thevolatile plasticiser is propionamide.

5. The hair control preparation as claimed in claim 2, wherein thevolatile plasticiser is selected from the group consisting of benzoicacid and salicylic acid.

6. The hair control preparation as claimed in claim 3, wherein thevolatile plasticiser is propionamide.

7. The hair control preparation as claimed in claim 1, additionallycomprising an aerosol propellant.

8. A process for treating human hair to impart hold to a desired styleand subsequently to facilitate the brush-out property of the hair as thehold diminishes, which process includes the step of applying to the haira hair control preparation as claimed in claim 1.

2. The hair control preparation as claimed in claim 1, wherein the resinis a copolymer of vinyl pyrrolidone and vinyl acetate containing atleast 70 percent by weight of vinyl acetate.
 3. The hair controlpreparation as claimed in claim 1, wherein the resin is a copolymer ofvinyl acetate and crotonic acid.
 4. The hair control preparation asclaimed in claim 2, wherein the volatile plasticiser is propionamide. 5.The hair control preparation as claimed in claim 2, wherein the volatileplasticiser is selected from the group consisting of benzoic acid andsalicylic acid.
 6. The hair control preparation as claimed in claim 3,wherein the volatile plasticiser is propionamide.
 7. The hair controlpreparation as claimed in claim 1, additionally comprising an aerosolpropellant.
 8. A process for treating human hair to impart hold to adesired style and subsequently to facilitate the brush-out property ofthe hair as the hold diminishes, which process includes the step ofapplying to the hair a hair control preparation as claimed in claim 1.